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Asymmetric Synthesis of β‐Substituted α‐Methylenebutyro‐ lactones via TRIP‐Catalyzed Allylation: Mechanistic Studies and Application to the Synthesis of ( S )‐(−)‐Hydroxymatairesinol
Author(s) -
Fuchs Michael,
Schober Markus,
Orthaber Andreas,
Faber Kurt
Publication year - 2013
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201300392
Subject(s) - chemistry , moiety , catalysis , phosphoric acid , aldehyde , yield (engineering) , enantioselective synthesis , asymmetric induction , ring (chemistry) , natural product , zinc , organic chemistry , stereochemistry , combinatorial chemistry , medicinal chemistry , materials science , metallurgy
Asymmetric allylation of (hetero)aromatic aldehydes by a zinc(II)‐allylbutyrolactone species catalyzed by a chiral BINOL‐type phosphoric acid gave β‐substituted α‐methylenebutyrolactones in 68 to >99% ee and 52–91% isolated yield. DFT studies on the intermediate Zn 2+ ‐complex – crucial for chiral induction – suggest a six‐membered ring intermediate, which allows the phosphoric acid moiety to activate the aldehyde. The methodology was applied to the synthesis of the antitumour natural product ( S )‐(−)‐hydroxymatairesinol.